Coating methods of hardenable multilayer arrangements

ABSTRACT

THIS INVENTION RELATES TO AN IMPROVED METHOD OF COATING UPON A SUPPORT SEVERAL SUPERIMPOSED DISTINCT LAYERS COMPRISING HARDENABLE ORGANIC HYDROPHILIC COLLOID AND A VINYLSULFONYL ALKYL HARDENER. THE IMPROVEMENT COMPRISES ADDING THE VINYLSULFONYL ALKYL HARDENER TO LESS THAN ALL THE LAYERS OF THE HARDENABLE ORGANIC HYDROPHILIC COLLOID TO UNIFORMLY HARDEN ALL THE HARDENABLE ORGANIC HYDROPHILIC COLLOID IN ALL THE LAYERS.

'UnitedStates Patent Oflice 3,687,707 Patented Aug. 29, 1972 3,687,707 COATING METHODS OF HARDENABLE MULTILAYER ARRANGEMENTS James Leo Graham, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y. No Drawing. Filed Apr. 29, 1970, Ser. No. 33,046 Int. Cl. G03c 1/30, N74

US. Cl. 117-34 12 Claims ABSTRACT OF THE DISCLOSURE This invention relates to an improved method of coating upon a support several superimposed distinct layers comprising hardenable organic hydrophilic colloid and a vinylsulfonyl alkyl hardener. The improvement comprises adding the vinylsulfonyl alkyl hardener to less than all the layers of the hardenable organic hydrophilic colloid to uniformly harden all the hardenable organic hydrophilic colloid in all the layers.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to a method of coating multilayer, photographic materials. In one aspect it relates to processes for coating multilayer, multicolor coupler forming photographic elements whose layers comprise hydrophilic colloids hardenable by vinylsulfonyl hardeners. In another aspect it relates to improved coating methods whereby superimposed multiple layers of a photographic silver halide element are all substantially hardened by differentially combining a hardener in certain of said layers.

There are many instances in the photographic art and particularly the coating art where it is necessary to apply multiple layers of coated materials so that the final product comprises a plurality of distinct superimposed layers. Depending on the element involved, the different coated layers generally perform individual and separate functions so that it is necessary that the distinct nature of each of said layers be maintained. Further, while non-contamination or non-diffusion of adjacent layers and their contents is often required, certain functions or structural requirements are in fact applicable to all of said layers.

One such example in a multiple layered photographic element such as film or paper and the like, is the treatment of the various hydrophilic colloid layers coated over the support. These layers, while providing a variety of functions are usually superimposed by a variety of coating methods whereby the individuality and identity of each layer is maintained While still insuring a rapid rate of coating. As an example, even a simple photographic film consists of numerous such coatings such as a light sensitive emulsion layer, with an abrasion-protecting overcoat, a thin subcoat in order to promote adhesion and still other specific coatings. When one considers the complexity of multi-coupler color-forming photographic elements in which still more coatings are employed, the need for distinct layer arrangement becomes more apparent. For example, the red, blue and green-sensitive emulsion layers and their color filtering coatings cannot be permitted to diffuse into each other.

Even after coating, particular care must be taken to insure that this photographic element containing said complex layer arrangement, is able to provide the recorded image after processing. Proper and adequate hardening of the colloid-containing layers becomes an essential part of the technique and art required for image production. As a matter of fact, in view of the high humidity encountered during storage, and elevated temperatures of the processing solutions, substantial hardening is required. However, while such physical protection against abrasion and loss of integrity leading to reticulation or excessive swelling are achieved by hardening the layers, a high degree of layer permeability must still be achieved in order to permit adequate penetration by the processing solutions.

It is not surprising, therefore, that in the past those skilled in the art have sought to uniformly harden multilayer photographic elements by the uniform addition of suitable hardeners to each of the melted coated solutions. For example, US. Pat. 2,652,345 issued to Jones on Sept. 15, 1953, adds a hardener to the coating solution prior to said hardener's activation.

In Russell US. Pat. 2,761,791 issued Sept. 4, 1956, methods of simultaneous coating of colloids in distinct layer arrangements are disclosed. A preferred method of hardening said layers coated in such a manner appears to be restricted to two coating layers hardened by the pH activation of an aldehyde-hardener, such as formaldehyde.

In contrast thereto, the present invention is directed to more complex multiple layers such as those comprising four or more superimposed layers hardened by a vinylsulfonyl alkyl hardener as more fully set forth hereafter. Further, it has been found that still other methods of simultaneous coating can be efiectively employed in the practice of the present invention such as those described in British Pats. 929,905 and 837,095 issued to Ilford on June. 26, 1963 and June 9, 1960 respectively. In addition. other suitable coating methods are described in British Pats. 1,143,931 and 1,159,598 issued to Fuji on Feb. 26, 1969 and July 30, 1969 respectively. Also, Within the contemplation of the present invention are a variety of other coating techniques such as the curtain coating technique described in Belgian Pat. No. 733,012 issued Nov. 13, 1969 to Hughes. In each of these methods, the problems of achieving uniform hardening is substantial and it is not surprising that corrective methods have been developed such as that described in US. Pat. 2,912,343 issued Nov. 10, 1959 to Collins wherein the hardener is mixed with the coating solution immediately prior to coating in order to reduce premature and uneven hardening. Even so, many hardeners tend to migrate and wander from one layer to another so that highly significant differences in the degrees of hardness may still exist among said multi layer coatings.

STATEMENT OF PROBLEM In multilayer photographic elements, and particularly those highly complex layer arrangements containing multicolor forming dye couplers, contained in hardenable c01- loid layers, the problem of elfectively hardening all of those layers within the delicate degree required of each, and in relation to each other, is difficult and costly since so many process steps are required. Further, insufficient hardening in any one layer causes hardener concentration gradients which result in unwanted varying degrees of diffusion of processing baths. Heretofore, the solution to this problem has involved adding to each melted coating layer the precise concentration calculated to achieve hardening.

In some cases pre-hardener solutions and other preparatory steps were required before coating. The greater the number of addenda and/ or process steps employed in preparing photographic elements and emulsion, the greater the risk of obtaining undesirable and adverse sensitometric values.

It is, therefore, believed that the present invention solves, by novel and unobvious means, a recurring problem which has heretofore been unresolved in the photographic art.

A method of providing substantially uniform hardening of the various hardenable layers of a multilayer photographic element which method is safe, economical and effective would be of significant value to the photographic art. Nowhere in the prior art does there appear the simple, time-saving and photographically superior process described hereafter.

Many inorganic and organic compounds are known in the art to be effective in hardening hydrophilic-colloids and include such hardeners as the aldehydes, blocked aldehydes, ketones, aziridines, carbodiimides and the like. The vinylsulfonyl hardeners found particularly eifective in the present invention are effective in hardening proteins such as natural polymers like gelatin and also synthetic carboxy-containing polymers as disclosed in Belgian Pat. 723,806 issued to Burness Jan. 15, 1969. However, high speed multiple layer coatings, as more fully described heretofore, present unique problems of handling, premature and unwanted hardening of non-uniform degree, poor sensitometry and numerous other problems which have not heretofore been solved.

It is an object of the present invention to provide a novel process for the coating of multilayer arrangements of distinct superimposed layers which layers are unexpectedly and substantially hardened uniformly in more effective, efiicient and economical means than those presently employed.

It is another object of this invention to combine, in less than all of the hardena'ble hydrophilic colloid layers a particular class of hardeners which uniquely provides a substantially uniform degree of hardening.

It is still another object of this invention to provide an improved multilayer, multicoloncoupler containing a photographic element which exhibits superior sensitometric properties able to faithfully reproduce a photographic image at high temperature processing.

Other objects of the invention will become apparent to those skilled in the art from an examination of the specification and claims which follow.

DESCRIPTION OF PREFERRED EMBODIMENT In accordance with the present invention, the above and still other objects are attained by employing improved coating methods utilizing a particular class of hardening agents in less than all of the coating melts for the multilayer arrangement which arrangement comprises at least four superimposed distinct layers.

The class of hardeners found particularly useful in the practice of this invention has the structural formula:

(CHFCHSO CH CH A Z in which A is or O, R being an alkyl of 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl and the like. X is an acid anion, Z is a polyvalent radical of n-valences and n is an integer in the range of 2 to 6, or

where m is 1 to 4 and Z is oxygen or nitrogen and R is lower alkyl or hydrogen.

A Wide variety of compounds within this class have been found to be particularly effective in achieving the degree of hardening required and include the following partial listing:

bis( 2-vinylsulfonylethyl) ether bis 4-vinylsulfonylbutyl) ether N,N-bis( 2-vinylsulfonylethyl -n-propylamine A particularly suitable bis-vinylsulfonylalkyl compound is bis(vinylsulfonylmethyl)ether having the formula:

(CHFCHSO CH In addition, other compounds such as the tris-, tetra-, penta-, and the like compound configurations are equally suitable.

The vinylsulfonyl alkyl hardeners react with a wide variety of amine-containing polymers, both natural and synthetic, such as gelatin, modified gelatin, and various polymers which are gel-compatible. These organic polymers are hydrophilic colloids which are used in a multitude of ways in the photographic art, for example, as a hinder or dispersant for silver halide grains.

In one embodiment of this invention, the grains of the silver halide layer are surface sensitized, converted halide, silver halide grains in which the halide comprises at least 50 mole percent bromide. A silver halide-containing layer is one of at least four of the superimposed distinct layers comprising the layer arrangement, and all of said layers are substantially hardened by combining during coating onto the support bearing said arrangement, a bis(vinylsulfonyl)alkyl hardener.

Another embodiment of this invention relates to coating onto a support such as a resin coated paper support, a multilayer arrangement of at least four superimposed distinct layers comprising hardenable organic hydrophilic colloids and a vinyl sulfonyl alkyl hardener, the improvement comprising utilizing a simultaneous coating procedure, in which the hardener is combined in less than all of the layer coating melts or reservoirs just prior to coating.

SUMMARY OF THE INVENTION There has now been discovered a significant improvement in methods of coating onto a support a multilayer arrangement of at least four superimposed distinct layers comprising hardenable organic hydrophilic colloids. The improvement utilizes a 'vinylsulfonyl alkyl hardener combined in less than all of the layers to be hardened. This method surprisingly achieves substantially uniform hardening without unwanted and undesirable sensitometric results.

While specific advantages are disclosed in multicolorcoupler containing elements and, in particular, surfacesensitized converted halide silver halide grain-containing elements, the present invention has wide applicability in the photographic art.

One unexpected result of the high efficiency of these vinylsulfonyl alkyl hardeners in the practice of this invention is the added protection against actually blowing off the wet coating from its support during the drying stage by the action of the drying jets at very high coating speeds, e.g., greater than 200 ft./min.

In still another embodiment of this invention a resincoated paper support bears a multilayer arrangement comprising distinct superimposed silver halide-containing layers useful in multicolor image formation. In particular these layers are sensitive respectively to blue, green and red, said layers containing color-forming dye couplers capable of forming, respectively, yellow, magenta, and cyan dyes upon color development. The red-sensitive layer, which contains the cyan forming color coupler, is, in one embodiment, the outermost light sensitive layer and the hardening compound is initially combined in a gelatin-containing interlayer coating melt between the blue-sensitive and green-sensitive layers, and between the green-sensitive and red-sensitive layers respectively, said hardening compound being present in a concentration from about 0.5% to about 3% based on the total weight of the gelatin in all the layers to be hardened. This embodiment includes the improvement whereby substantial hardening of the gelatin layers is achieved by combining in less than all of said layers the vinylsulfonyl alkyl hardeners described herein.

In yet another embodiment, the multilayer arrangement comprises distinct superimposed silver halide graincontaining layers sensitive, respectively, to blue, green and red, the layers containing color-forming dye couplers capable of forming, respectively, yellow, magenta and cyan dyes upon color development. The blue sensitive layer contains yellow-forming color coupler and is the outermost light senstive layer. The hardening compound is combined in a concentration range of about 0.5 to about 3% based on the total hardenable colloid, such as the gelatin contained in the layers.

In still another embodiment, the vinylsulfonyl alkyl hardener is bis(vinylsulfonylmethyl)ether and is differentially combined from the coating melt of (1) a gelatin containing interlayer, (2) a cyan-forming color couplercontaining layer, (3) a gelatin-containing interlayer between a magenta dye-forming color coupler-containing layer and a Carey-Lea silver-containing layer and (4) a cyan and yellow dye-forming color coupler-containing layer, said layers representing less than all of the arranged multiple layers, which are finally substantially uniformly hardned by said hardener.

The vinylsulfonyl alkyl hardeners used in the practice of this invention are prepared by means well known in the art such as more fully described in Belgian Pat. 723,806 issued Jan. 15, 1969 to Burness et al. Once obtained, the vinylsulfonyl alkyl hardeners are conveniently added to the coating solutions from various aqueous or organic solvent solutions. A variety of methods of blending the sulfonyl-containing solution to the coating mixtures can be employed, such as, for example, blending immediately prior to coating with constant or intermittent stirring.

It has been found desirable to reduce the time the hardener is permitted to remain in contact with the liquid coating solutions, such as the gelatin-containing emulsions. Typical of processes useful therefor include those taught by US. Pat. 3,342,605 issued Sept. 19, 1967 to McCrossen et al. and US. Pat. 3,425,835 issued Feb. 4, 1969, to Johnson et al. While it has been found that some hardeners can be simply added to the solution, the risk of unwanted coagulation of colloidal particles is ever-present due to protracted holding time before coating. The process of U.S. Pat. 2,912,343 of Collins et al. issued Nov. 10, 1959 teaches certain methods to obviate said problem.

As set forth hereinbefore, a variety of coating techniques can be employed in preparing and coating the multilayer elements which are improved by the present invention. Likewise, a variety of supports can be employed over which the superimposed layers are coated. Typical of these relatively flexible supports include such supports as cellulose nitrate film, cellulose ester, polyester, poly(vinylacetal), polycarbonates, and various related films including a great variety of resinous materials, as well as more rigid supports such as glass, cardboard, metal and the like. A desirable flexible support is comprised of paper easily acetylated, partly or totally, or baryta-coated and/or a-olefin polymer coated.

In such cases, a preferred polymer film comprises an a-olefin-containing from 2 to carbon atoms and includes for example the poly-ethylene, polypropylene, ethylenebutene copolymers and the like. It is known that paper supports, the surfaces of which have been overcoated with an a-olefin polymer, especially an a-olefin such as polyethylene, can be further treated to improve their properties such as by electron bombarding prior to coating or in-line electron bombarding during the coating operation as more fully described in British Pat. 1,043,703 of Kemp issued Sept. 21, 1966. These particular processes tend to improve the adhesion of hydrophilic colloid layers, especially gelatin layers, coated on the support.

While a great number of hardening agents have been used heretofore in attempts to substantially and uniformly harden the various multiple layers, far less complex than those described, the particular and unexpected advantages set forth herein have not been achieved before.

The vinylsulfonylalkyl hardeners used herein are effective in a broad range of concentrations, such as from about 0.25% to about 6.0% by weight of hardenable 6 material. They are particularly effective at concentrations from about 0.5% to about 3.0% by weight based on hardenable material.

It will be understood by those skilled in the art that the term differential as used to describe combining or adding of said class of hardeners, is an unequal distribution to other than each and every layer at the outset of the coating operation. In still another way of describing said addition, it can be said to be selective in that one can predetermine the particular coating layer melts or reservoirs to which are added said hardener. In terms of the layer arrangement, the hardener can be added to said layers both symmetrically and asymmetrically so long as less than all layers or their coating solutions initially contain said hardener.

By the term superimposed, it will be understood by those skilled in the art to mean those coated layers which are placed or laid over each other in direct or indirect contact, i.e. in a series of such layers where they are positioned in an immediate or mediate contiguous fashion.

While the exact reasons for the substantially uniform hardening results obtained are unknown, it can only be presumed at this time that the diffusion and migration patterns of the vinylsulfonylalkyl hardeners are oriented in such an unexpected way as to achieve the results set forth in a substantially uniform pattern.

This is all the more remarkable considering the complex variations, for example, in colloid, silver halide and addenda content from layer to layer. Examplary of one preferred embodiment is the layer arrangement comprised of the following complex layers set forth in their respective superimposed coating patterns as follows:

(1) First layer arrangement (a) gray-silver antihalation undercoat,

(b) gelatin pad containing about 0.50% to about 3.0% by total weight of gelatin of bis(vinylsulfonylmethylor ethyl)ether in the first set of layers, added just prior to coating;

(2) Second layer arrangement (a) a slow, red-sensitive silver halide emulsion layer containing a phenolic or naphtholic cyan dye-forming coupler,

(b) a fast, red-sensitive silver halide emulsion containing a phenolic or naphtholic cyan dye-forming coupler and about 0.50% to about 3.0% bis(vinylsulfonylmethylor ethyl)ether by total weight of gelatin in the second set of layers added just prior to coating,

(0) a gelatin interlayer;

(3) Third layer arrangement (a) a slow, green-sensitive silver halide emulsion containing a S-pyrazolone magenta dye-forming coupler, (b) a fast, green-sensitive silver halide emulsion iayer containing a magenta 5-pyrazolone dye-forming coupler,

(c) a gelatin interlayer containing from 0.50% to about 3.0% bis(vinylsulfonylmethyl or ethyl)ether by total weight of gelatin in the third set of layers added just prior to coating,

(d) a Carey-Lea silver interlayer;

(4) Fourth layer arrangement (a) a slow blue-sensitive silver halide emulsion containing a ketomethylene open-chain yellow dye-forming coupler,

(b) a fast blue-sensitive silver halide emulsion containing a ketomethylene open-chain yellow dye-forming coupler and from about 0.50% to about 3.0% bis(vinylsulfonylmethyl or ethyl)ether by total weight of gelatin in the fourth set of layers added just prior to coat- (c) a gelatin overcoat.

Thus, it is seen that the use of the term multilayer arrangement is used to describe a highly complex system and configuration of superimposed coatings whose placement and position as to each other is critical for producing the desired results. Said layers are distinct in that they re tain their individual character and layer integrity.

By use of the term uniform it will be understood to mean the same relative degree of hardness or resistivity to melting of the hardenable colloids in the varying layers regardless of the difference in layer thickness, addenda content or total colloid content in any of said layers.

In another embodiment of the present invention a sixlayer coated arrangement comprising the following configuration is improved in the practice of the present invention:

( 1) a blue-sensitive silver halide emulsion next to the support, containing a ketomethylene open-chain yellow dye-forming coupler,

(2) a gelatin interlayer containing from about 0.5 to about 3.0 bis(vinylsulfonylmethyl or ethyl)ether by total weight of gelatin in all six layers, is added just prior to coating,

(3) a green-sensitive silver halide emulsion containing a magenta dye-forming -pyrazolone coupler,

(4) an ultraviolet light absorbing gelatin interlayer,

(5) a red-sensitive silver halide emulsion containing a cyan dye-forming phenolic or naphtholic coupler, and

(6) a gelatin overcoat.

Among various supports useful in such arrangement is a resin coated support, especially a polyethylene treated paper support, electron-bombarded preferably not more than about 24 hours prior to coating time. Where in-line bombardment is employed, that is, during the coating procedure, a polyethylene treated paper support bears the following superimposed configuration with unexpected substantially uniform hardening:

(1) a blue-sensitive silver halide emulsion adjacent to the support containing a ketomethylene open-chain yellow dye-forming coupler,

(2) next, a gelatin interlayer containing from about 0.50% to about 3.0% bis(vinylsulfonyhnethyl or ethyl)ether by total weight of gelatin in all six layers added just prior to coating,

(3) a green-sensitive silver halide emulsion containing a magenta dye-forming 5-pyrazolone coupler,

(4) an ultraviolet light absorbing gelatin interlayer containing from about 0.50% to about 3.0% bis(vinylsulfonylmethyl or ethyl)ether by total weight of gelatin contained in all six layers added just prior to coating,

(5) a red-sensitive silver halide emulsion containing a cyan dye-forming phenolic or naphtholic coupler, and

(6) a gelatin overcoat,

While in one preferred aspect, it is desirable to place the vinylsulfonylalkyl hardeners in that particular layer containing the least concentration of organic hydrophilic colloid, such as gelatin, any series of combinations at various times is believed within the eifective scope and contemplationot this invention. For example, it is preferred, in an element containing an arrangement of four or more layers, coated out in separate and different coating passes, to combine the hardener immediately prior to coating in the first or second layer of the last layer arrangement. Maximum and substantially uniform hardness is achieved in this manner as contrasted with less desirable and less effective uniform coating or hardeners.

That the present process provides unexpected results and highly useful application is shown in part by the examples set forth hereafter.

Typical of the complex coated elements prepared by the processes of the present invention is a photographic multilayer element which comprises a bis(vinylsulfonyl)alkyl hardened hydrophilic colloid containing in superimposed fashion coated over a flexible support: (1) a first silver halide emulsion sensitive to one region of the visible spectrum and contiguous thereto, a non-diffusible ketomethylene open-chain yellow dye-forming coupler which reacts with oxidized primary aromatic amine color developing agent forming a yellow dye, and (2) a second silver halide emulsion sensitive to another region of the visible spectrum and contiguous thereto a non-diffusible 5pyrazolone coupler which reacts with oxidized primary aromatic amine color developing agent forming a magenta dye. In addition to the first and second silver halide emulsions described above, the photographic element contains still another silver halide emulsion coated thereover sensitive to a third region of the visibe spectrum and contiguous thereto a non-diffusible phenolic or naphtholic coupler which reacts with oxidized primary aromatic amine color developing agents to form a cyan dye. Other arrangements of the light sensitive layers are also known, e.g., the emulsion layers can be double-coated as described in British Pat. 923,045, issued to Agfa on Apr. 10, 1963.

A particularly useful modification of the present invention comprises the process of coating and hardening multilayer, multicolor, coupler-containing, photographic printing element, designed to produce reflection color prints. Said element comprising a resin coated paper support, especially an electron-bombarded polyethylene treated paper support. This element is successively coated with a blue-sensitive silver halide emulsion containing a ketomethylene open-chain yellow dye-forming coupler, a gelatin containing interlayer, a green sensitive silver halide emulsion containing a magenta dye-forming coupler, an ultraviolet absorbing gelatin containing interlayer, a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler and a gelatin-containing overcoat as described in U.S. Pat. 2,956,879 issued Oct. 18, 1960 to Van Campen. Still other arrangements of the sensitive layers are also included in the present invention and the element likewise can have other interlayers for specialized purposes such as antihalation, overcoat, subbing layers and the like.

The various photographic elements such as printing materials coated by the process of this invention and processed after exposure are particularly acceptable when developed in an aqueous alkaline solution in the presence of a primary aromatic amine color developing agent, followed by silver halide solvent and an oxidizing agent for silver. A water wash can be used sometimes immediately after the development, followed by washing and drying or washing and then stabilization with a bath before drying. Vinylsulfonylalkyl hardened multilayer, multicolor-coupler forming photographic film elements coated by the process of this invention can likewise be processed in a color reversal process such as the Eastman Kodak ME4 process without a pro-hardener solution or in a color negative process such as the Kodak C-22 process.

The various organic, hardenable hydrophilic colloids useful in the emulsions, photographic elements and various layers prepared by the processes of the present invention can be employed alone or in combination. Suitable hydrophilic materials include both naturally-occurring substances such as proteins, for example, gelatin, modified gelatin and gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances, such as water soluble polvinyl compounds like poly(vinylpyrrolidone), acrylamide polymers and the like.

The described photographic emulsion layers and other layers of a photographic element employed in the practice of this invention can also contain, alone or in combination with hydrophilic, water permeable colloids. Still other synthetic polymeric compounds such as dispersed vinyl compounds such as in latex form and particularly those which increase the dimensional stability of the photographic materials. Suitable synthetic polymers include those described, for example, in Nottorf U.S. Pat. 3,142,568 issued July 28, 1964; White U.S. Pat. 3,193,- 386 issued July 6, 1965; Houck et al. U.S. Pat. 3,065,674 issued Nov. 6, 1962; Houck et al. U.S. Pat. 3,220,844 issued Nov. 30, 1965; Ream et al. U.S. Pat. 3,287,289 issued Nov. 22, 1966; and 'Dykstra U.S. Pat. 3,411,911 issued Nov. 19, 1968; particularly effective are those water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacry-- lates, those which have cross-linking sites which facilitate hardening or curing, those having recurring sulfobetaine units as described in Dykstra Canadian Pat. 774,054 issued Dec. 19, 1967.

The various hydrophilic colloid layers of the above described photographic elements, coated by the process of this invention, can contain hardening agents, such as, aziridine hardeners, isoxazolium salt hardeners, and epoxide compounds in addition to the vinylsulfonyl al'kyl hardeners described herein.

The silver halide emulsions used with this invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof. The term converted-halide silver halide grains employed herein is well known to those skilled in the art. This term relates to silver halide grains, prepared in a variety of ways, such as by first forming an emulsion or dispersion of silver salt grains consisting at least in part of a silver salt more soluble in water than silver bromide, and then converting at least a portion of said salt grains to silver bromide or bromoiodide salts as more fully described in U.S. Pat. 2,592,250 of Davey et al. issued Apr. 8, 1952. The emulsions can be prepared by any of the well-known procedures, and can include various emulsion types such as single jet, double jet, Lippmann, ammoniacal, thiocyanate or thioether ripened emulsions and those described in Nietz et al. U.S. Pat. 2,222,264 issued Nov. 19, 1940; Illingsworth U.S. Pat. 3,320,069 issued May 16, 1967; and McBride U.S. Pat. 3,271,157 issued Sept. 6, 1966. Surface image emulsions can be used as well as internal image emulsions such as those described in Davey et al. U.S. Pat. 2,592,250 issued May 8, 1952; Porter et al. U.S. Pat. 3,206,313 issued Sept. 14, 1965; Berriman U.S. Pat. 3,367,778 issued Feb. 6, 1968; and Bacon et al. U.S. Pat. 3,447,927 issued June 3, 1969. If desired, mixtures of surface and internal image emulsions can be used as described in Luc-key et al. U.S. Pat. 2,996,382 issued Aug. 15, 1961. Negative type emulsions or direct positive emulsions can be used such as those described in Leermakers U.S. -Pat. 2,184,013 issued Dec. -19, 1939; Kendall et al. U.S. Pat. 2,541,472 issued Feb. 13, 1951; Berriman U.S. Pat. 3,367,778 issued Feb. 6, 1968; Schouwenaars British Pat. 723,019 issued Feb. 2, 1955; Illingsworth et al. French Pat. 1,520,821 issued Mar. 4, 1968; Ives U.S. 'Pat. 2,563,785 issued Aug. 7,

1951; Knott et al. U.S. Pat. 2,456,953 issued 'Dec. 2 1, 1948 and Land U.S. Pat. 2,861,885 issued Nov. 25, 1958. The emulsions can be regular grain emulsions such as the type described in Klein and Moisar, J. Phot. Sci., vol. 12, No. 5, September/October 1964, pp. 242-251.

The silver halide emulsions used with this invention can be unwashed or washed to remove soluble salts. In the latter case the soluble salts are removed by chill-setting and leaching or the emulsion is coagulation Washed, e.g. by the procedures described in Hewitson et al. U.S. Pat. 2,618,556 issued Nov. 18, 1952; Yackel U.S. Pat. 2,565,418 issued Aug. 21, 1951; Hart et al. U.S. Pat. 3,241,969 issued Mar. 22, 1966; and Waller et al. UJS- Pat. 2,489,341 issued Nov. 29, 1949.

The emulsions used with this invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these. Suitable procedures are described in Sheppard et al. U.S. Pat. 1,623,499 issued Apr. 5, 1927; Waller et al. U.S. Pat. 2,399,083 issued Apr. 23, 1946; McVeigh U.S.

10 Pat. 3,297,447 issued Jan. 10, 1967; and Dunn U.S. Pat. 3,297,446 issued Jan. 10, 1967.

The silver halide emulsions used with this invention can contain speed increasing compounds such as poly alkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper US. Pat. 2,886,437 issued May 12, 1959; Damn et al. U.S. Pat. 3,046,134 issued July 24, 1962; Carroll et al. U.S. =Pat. 2,944,900 issued July 12, 1960; and Goffe U.S. Pat. 3,294,540 issued Dec. 27, 1966.

The silver halide emulsions used in the practice of this invention can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping. Suitable antifoggants and stabilizers each used alone or in combination include thiazolium salts described in Brooker et al. U.S. Pat. 2,131,038 issued Sept. 27, 1938 and Allen et al. U.S. Pat. 2,694,716 issued Nov. 16, 1954; the azaindenes described in Piper U.S. Pat. 2,886,437 issued May 12, 1959; and Heimbach et al. US. Pat. 2,444,605 issued July '6, 1948; the mercury salts as described in Allen et al. U.S. Pat. 2,728,663 issued Dec. 27, 1955; the urazoles described in Anderson et al. U.S. Pat. 3,287,135 issued Nov. 22, 1966; the sulfocatechols described in Kennard et al. U.S. Pat. 3,236,652 issued Feb. 22, 1966; the oximes described in Carroll et al. British Pat. 623,448 issued May 18, 1949; nitron; nitroindazoles; the mercaptotetrazoles described in Kendall et al. U.S. Pat. 2,403,927 issued July 16, 1946; Kennard et al. U.S. Pat. 3,266,897 issued Aug. 16, 1966 and Luckey et al. U.S. Pat. 3,397,987 issued Aug. 20, 1968; the polyvalent metal salts described in Jones U.S. Pat. 2,839,405 issued June 17, 1958; the thiuronium salts described in Herz et al. U.S. Pat. 3,220,839 issued Nov. 30, 1965; the palladium, platinum and gold salts described in Trivelli et al. U.S. Pat. 2,566,263 issued Aug. 28, 1951 and Yutzy et al. U.S. Pat. 2,597,915 issued May 27, 1952.

The photographic layers employed in the practice of this invention can contain plasticizers and lubricants such as polyalcohols, e.g. glycerin and diols of the type described in Milton et al. U.S. Pat. 2,960,404 issued Nov. 15, 1960; fatty acids or esters such as those described in Robijns U.S. Pat. 2,588,765 issued Apr. 11, 1952 and Duane U.S. Pat. 3,121,060 issued Feb. 11, 1964; and silicone resins such as those described in Du Pont British Pat. 955,061 issued Apr. 15, 1964.

The photographic layers employed in the practice of this invention can contain surfactants such as saponin; anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. 2,600,831 issued June 17, 1952; amphoteric compounds such as those described in Ben-Ezra U.S. Pat. 3,133,816 issued May 19, 1964: and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British 1,022,878 issued Mar. 16, 1966.

Spectral sensitizing dyes can be used conveniently to confer additional sensitivity to the light sensitive silver halide emulsion of the multilayer photographic elements of the invention. For instance, additional spectral sensitization can be obtained by treating the emulsion with a solution of a sensitizing dye in an organic solvent or the dye can be added in the form of a dispersion as described in Owens et al. British Pat. 1,154,781 issued June 11, 1969. For optimum results, the dye is either added to the emulsion as a final step or at some earlier stage.

Sensitizing dyes useful in sensitizing such emulsions are described, for example, in Brooker et al. U.S. Pat. 2,526,632 issued Oct. 24, 1950; Sprague U.S. Pat. 2,503,- 776 issued Apr. 11, 1950; Brooker et a1, U.S. Pat. 2,493,- 748 issued Jan. 10, 1950; and Taber et a1. U.S. Pat. 3,384,486 issued May 21, 1968. Spectral sensitizers which can be used include the cyanines, merocyanines, complex (tri or tetranuclear) merocyanines, complex (tri or tetranuclear) cyanines, holopolar cyanines, styryls, hemicy- 11 anines (e.g. enamine hemicyanines), oxonols and hemioxonols.

Dyes of the cyanine classes can contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles. Such nuclei can contain alkyl, alkylene, hydroxyalkyl, sulfu alkyl, carboxyalkyl, aminoalkyl and enamine groups and can be fused to carbocyclicor heterocyciic ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, c'yano, or alloxy groups. The dyes can be symmetrical or unsymmetrical and can contain, alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain.

The merocyanine dyes can contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile. These acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkyamino groups, or heterocyclic nuclei. Combinations of these dyes can be used, if desired. In addition, supersensitizing addenda which do not absorb visible light can be included, for example, ascorbic acid derivatives, azaindenes, cadmium salts, and organic sulfonic acids as described in McFall et al. U.S. Pat. 2,933,390 issued Apr. 19, 1960 and Jones et a1. U.S. Pat. 2,937,089 issued May 17, 11960.

The various layers, including the photographic layers, employed in the practice of this invention can contain light absorbing materials and filter dyes such as those described in Sawdey US. Pat. 3,253,921 issued May 31, 1966; Gaspar U.S. Pat. 2,274,782 issued Mar. 3, 1942; Silberstein et al. US. Pat. 2,527,583 issued Oct. 31, 1950 and Van Campen US. Pat. 2,956,879 issued Oct. 18, 1960. If desired, the dyes can be mordanted, for example, as described in Milton et al. US. Pat. 3,282,699 issued Nov. 1, 1966.

Any non-diirusible ketomethylene open-chain yellow dye-forming coupler that reacts with primary aromatic amine color developing agents to form a yellow dye is advantageously used in our photographic materials. These couplers include all of the well-known non-difiusing openchain ketomethylene yellow dye-forming couplers including those that have a coupling-01f group substituted on the active carbon atom.

Typical couplers as described include the following:

( 1 rx- 1-phenyl-5-tetrazolylthio) a-pivalyl-2-chloro- 2,4-di-tert-amylphenoxy) butyramido] acetanilide.

(2) a-pivalyloc- 4- carb oxyphenoxy) -2-chloro-5- ['y- (2,4-di-tert-amylphenoxy)butyrarnido] acetanilide.

(3 m- (pivaiyl -2-chloro-5- ['y(2,4-di-tert-amylphenoxy) butyramido] acetanilide.

(4) a-pivalyl-e-M- (p-benzyloxybenzenesulfonyl) phenoxy] -2-chloro-5- oz- 2,4-di-tert-amylphenoxy) butyramido] acetanilide.

( S a- [3-{04- 2,4-di-tert-amylphenoxy) butyramido} benzoyl] -2-methoxyacetanilide.

(6) oz-{3- [oz- (2,4-di-tert-amylphenoxy) acetamido] benzoyl}-2methoxyacetanilide.

Any of the known non-difl'usible S-pyrazolone coupiers are likewise incorporated to advantage in the photographic element. These couplers include those having the formulae:

12 wherein R represents an alkyl group (substituted or not), an aromatic group (substituted or not), a heterocyclic group (substituted or not), etc.; -R' represents a group such as an alkyl group, a carbamyl group, an amino group, an amide group (e.g. amido, a benzamido group, an allo amido group, etc.), and Y representsa coupling-oft group such as the thiocyano group, an acyloxy group, an aryloxy group, an alkoxy group, an alkylthio group, an arythio group, the chlorine atom, the fluorine atom, the sulfo group, etc. The R and/or R groups are advantageously substituted with any of the well-known substituent groups used in color-forming couplers including ballasting groups to render the couplers non-dilfusible in hydrophilic colloid layers, and solubilizing groups.

Examples of the magenta dye-forming couplers include the following:

( 1 1- (2,4, 6-trich1orophenyl) -3-{ 3-[a-( B-pentadecylphenoxy) -butyramido] benzamido}-5-pyrazolone.

(2 1- (2,4,G-trichlorophenyl)-3-p-methoxyphenylazo-4- [a- 2,4; di-tert-amylphenoxy) butyramido] anilino-S- pyrazolone.

(3 1- 2,4,6-trichlorophenyll -3- [Z-chloro-S- a-{4-hydroxy-3-tert-butylphenoxy}tetradecanoamido) anilinoJ- S-pyrazolone.

(4) 1- (2,4,6-trichlorophenyl) -3- [3-(2,4-diamylphenoxyacetamido -benzamido] -4-(4-methoxyphenylazo -S- pyrazolone.

(5 l- (2,4-dimethyl-6-chlorophenyl -3- [3-{u-(m-pentadecylphenoxy)butyramido}benzamido]-5-pyrazolone.

(6) 1-(2,4,6-trichlorophenyl) -3- [3-{04- (2,4-di-tertamylphenoxy) acetamido}benzamido] -5-pyrazolone.

Any of the well-known non-difiusible phenolic and naphtholic cyan dye-forming couplers are used to advantage in the practice of this invention. The cyan dye-forming couplers include those having the formulae:

OH. OH

RE Ra RI and R R Br R3 OH OH and R R R4 Y R in Y wherein R represents hydrogen, an alkyl group, an aryl group, a heterocyclic group, an amino group (e.g. amino, alkylamio, arylarnino, heterocyclic amino, etc.), a substituted canbonamido group (e.g. an alkylcarbonamido group, an arylcarbonamido group, and a heterocycliccarbonamido group), a substituted sulfonamido group (e.g. an alkylsulfonamido group, an arylsulfonamido group, a heter-ocyclicsulfonamido group, etc), a substituted sulfamyl group (e.g. an alkylsulfarnyl group, an arylsulfarnyl group, a heterocyclic sulfamyl group, etc.), a substituted carbamyl group (e.g. an alkylcarbamyl group, an arylcarbamyl group, a heterocyclic carbamyl group, etc.), etc.; R R and R each represent any of the groups represented by R and in addition the chlorine atom, an alkoxy group, etc.; R R R and R are advantageously further substituted by any of the ballasting groups well known in the art; Y represents the groups previously defined for Y but does not represent an aryloxy group; Y represents the groups previously defined for Y and also includes a cyclic imido group (e.g. a maleimidc group, a succinimido group, a 1,2-dicanboxylimido group, a phthalimido group, etc.)

Examples of these cyan-forming couplers include the following:

( 1 2- a-diamylphenoxy-n-butyrylamino -4,6-dich1oro- S-methylphenol.

( 2) l-hydroxy-N- (Z-n-tetradecyloxyphenyl) -4-( 1- phenyl-S -tetrazolyltl1io -2-naphthamide.

(3 1-hydroxy-4- (4- [2{8-acetamidol-hydroxy-3,6-

disulfonaphthyl}-azo] phenoxy) -2- a- [2,4-di-tert-amy1- phenoxy] butyl)naphthamide dipyridine salt.

(4) 1-hydroxy-4- 2-acetylphenylazo -N- [2,4-di-tertamyl-phenoxy) butyl] -2-naphthamide.

(5) 5- [oz- (2,4-di-tert-amylphenoxy) hexanamido] -2- heptafluorobutyramido phenol.

(6) 1-hydroxy-2-[A-(2,4-di-tert-amylphenoxy)-n-butyl]- naphthamide.

The couplers used in the practice of this invention are advantageously dispersed in the hydrophilic colloid by any of the techniques well known in the art. For example, dispersion can be effected in high-boiling crystalloidal compounds by methods such as described by Jelley and Vittum in US. Pat. 2,322,027 issued June 15, 1943. The couplers are advantageously dispersed in low solvent dispersions as described by Fierke in US. Pat. 2,801,171 issued June 30, 1957. Also applicable is dispersion in natural resin-type solvents as described by Martinez in US. Pat. 2,284,879 issued June 2, 1942, or solution in a monomeric solution, which is then polymerized in the presence of gelatin to produce dispersions of the coupler in the polymer as described in US. Pat. 2,825,382 issued Mar. 4, 1958. Fischer-type couplers are advantageously added to the hydrophilic colloid solution.

The following examples are included for a further understanding of the invention.

EXAMPLE 1 A multilayer, multicolor forming coupler containing photographic element well known in the prior art and comprising twelve layers suitably arranged for color processing is prepared by coating, on a cellulose acetate film support, several layer arrangements, for example arrange ment 1 contains layers 1 and 2, arrangement 2 contains layers 3 to 5, arrangement 3 contains layers 6 to 9 and arrangement 4 contains layers 10 to 12 1215 described in US. Pat. 2,761,791 of Russell issued Sept. 4, 1956. The final multilayer, multicolor forming coupler containing photographic element is of the general layer composition and structure as described in graphic FIG. 1.

FI G U RE 1 Layer 12 (dry over coat) Gelatin.

Layer 11 (fast yellow) AgBrI plus gelatin plus yellow-dye forming color coupler.

Layer 10 (slow yellow) Do.

Layer 9 (Carey-Lea silve Ag plus gelatin.

Layer 8 (interlayer) Gelatin.

Layer 7 (fast magenta) AgBrI plus gelatin plus magenta-deforming color coupler.

Layer 6 (slow magenta) Do.

Layer 5 (interlayer) Gelatin.

Layer 4 (fast cyan) AgBrI plus gelatin plus cyan-dye forming color coupler.

Layer 3 (slow cyan) Do.

Layer 2 (gel pad) Gelatin.

Layer 1 (antihalation) Gray Ag plus gelatin.

Cellulose acetate support The known gelatin hardener, mucochloric! acid, is added as follows to each liquid photographic emulsion prior to its actual coating: layers 1 to 11 each contain mucochloric acid at 0.27% by total weight of gelatin present in each layer; layer 12 contains mucochloric acid at a concentration of 2.15% by total weight of gelatin in the layer. A coated and hardened sample of this is kept for a period of 7 days at a temperature of 120 F. and 50% relative humidity and compared to a check control sample kept for 7 days at 40 F. and 50% relative humidity. Samples of the control and incubated elements are color processed in an Eastman Kodak ME-4 Process which includes a pre-hardener solution and in which the solutions are kept at F. The degree of swell of the gelatin layers is used as a measure of relative hardness and is determined for each element during the entire color processing sequence. Table I records these determinations and indicates the difference in degree of swell (A t) between the check control element and the incubated sample after the first developer step and at the end of the processing.

EXAMPLE 2 In order to provide data recording the degree of hardening, i.e. swelling of gelatin layers, when the vinylsulfonylalkyl hardener is added immediately prior to coating to all layers as conventionally done heretofore, the coating procedure described in Example 1 is repeated. Bis(vinylsulfonylmethyDether is added immediately prior to coating to each layer within each arrangement at a concentration of 2% by total weight of gelatin in each layer. A sample of this multilayer, multicolor coupler containing element is incubated and processed as described in Example 1 with the exception that no pre-hardener solution is employed. Table I contains the swell measurements obtained as described in Example 1.

EXAMPLE 3 In order to demonstrate one aspect of the present invention, less than all of the hardcnable layers are coated With a preferred hardener.

The coating procedure described in Example 1 is repeated with the exception that a representative hardener of the vinylsulfonylalkyl class, bis(vinylsulfonylmethyl) ether, is blended with the aqueous coating solutions just prior to coating as described in US. Pat. 2,912,343 of Collins et a1. (supra) and is added to the respective layer arrangements as follows all in a concentration of 2% of the total weight of dry gelatin present in each particular layer: in the first arrangement, containing layers 1 to 2, hardener is added to layer 2; in the next arrangement containing layers 3 to 5, hardener is added to layer 4; in the next superimposed layer arrangement containing layers 6 to 9, hardener is added to layer 8; and in the last layers superimposed thereover, hardener is added only to layer 11 among layers 10 to 12. A sample of this multilayer, multicolor coupler-containing element is incubated and processed as described in Example 1 with the exce tion that no pro-hardener solution is employed. Table I contains the various swell measurements and confirms that the hardest coating is made by adding the hardener just prior to coating and utilizing the simultaneous and selective multiple coating method of Example 3 whereby less than all layers contain hardener at time of coating.

15 EXAMPLE 4 In demonstrating that the present invention is advantageously utilized in coating photographic elements such as multilayer, multicolor coupler forming printing papers, several elements identified as A to G are prepared having a six layer arrangement coated on a paper support, which has been coated with polyethylene on both sides and whose surface has been electron bombarded approximately hours prior to the time of coating. This element com- 2, differing only in the type and concentration of hard ener and its initial location in the multilayer coatings. Table III lists six coated elements (A to F) where either mucochloric acid (shown as MA) or bis(vinylsulfonylmethylether (shown as VSE) as the hardening agent has been added just prior to coating in the manner described in Collins US. Pat. 2,912,343 (supra) to various layers in varying concentrations based on the total gelatin content. The vertical swell measurements obtained by the same procedure set forth in Example 4 are shown by Amp.

prises the layer composition and general graphic structure shown in FIG. 2.

FIGURE 2 Layer 6, dried overcoat Gelatin. Layer 5, cyan AgClBr plus gelatin plus cyan dye forming coupler.

Layer 4, ultraviolet absorben--- Gelatin plus ultraviolet absorber. Layer 3, magenta. AgGlBr plus gelatin plus magenta dye forming coupler.

Layer 2,interlayer Gelatin.

Layer 1, yellow-.-" AgClBr plus gelatin plus yellow dye forming coupler.

Support The hardening agent, bis(vinylsulfonylmethyl)ether is added immediately prior to coating in the manner described in U.S. Pat. 2,912,343 of Collins (supra) as shown to different layers in varying concentrations based on the total gelatin content. The results obtained are of vertical swell measurements shown as (Amy) subsequent to subjecting the coating to a 100 F. water bath. The maximum degree of swelling occurs after about 5 to seconds.

The results of Table 11 indicates that when all six layers are coated simultaneously, the preferred concentration of bis(vinylsulfonylmethyl)ether hardening agent is 1.00% by total weight of gelatin in all six layers and the preferred initial hardening location is in layer 2, i.e. the gel interlayer, shown by Example 4(c).

The several multicolor-coupler forming elements are imagewise exposed and color processed. The addition of the bis(vinylsulfonylmethyhether hardening agent is virtually devoid of any adverse sensitomertic effect, such as speed, maximum density or minimum density of the cyan, magenta or yellow layers.

TABLE II Total hardener concen- Percent hardener and Swell, Coated element tratiou 1 location A111);

1. 00 1.00, layer 1 36 0. 75 0.75, layer 1.-. 49 1. 00 lgyer g-.-

yer 0. :6 E gr 42 0 yer 75 {0.25: layer 4 i 44 0.25, layer 2- 0. 75 0.25, layer 4- 44 0.25, layer 6 4. 50 0.75, layers 1 to 6 (all) 43 Percent by total weight of gelatin in element.

EXAMPLE 5 The invention is further exemplified by tests conducted on multilayer, multicolor-coupler forming photographic printing papers prepared by coating all layers simultaneously as described in Russel US. Pat. 2,761,791 (supra). The support is paper coated with polyethylene on both sides and whose surface is in-line electron bombarded at the time of coating as more fully described in Kemp British Pat. 1,043,703 (supra). The graphic structural cross section of these elements is shown in previous FIG.

Table III shows that Example D, in which the hardening agent bis (vinylsulfonylmethyl)ether (VSE) has been added to the liquid photographic material just prior to coating during a simultaneous multilayer coating operation, unexpectedly provides the hardest photographic element as shown by the significant results obtained by the vertical swell testing.

As in Example 4, use of the hardener of this preferred class, i.e. bis(vinylsulfonylmethyhether shows no significant adverse sensitometric properties such as speed, maximum density or minimum density after color processing of all three layers.

EXAMPLE 6 In order to further demonstrate the unexpected and superior results afiorded by the present invention, two elements are prepared. One is like Example 1 herein where the hardener is added to each layer to be hardened at the coating stage and the other element is as described in Example 3 wherein the hardener is preferentially placed in less than all of the layers to be hardened.

Both elements are coated and dried at high speeds of the coated web in drying chambers where hot air is forced under pressure through numerous nozzle-outlets. At webcoating speeds of about ft./rninute both elements appear to dry satisfactorily while the multiple layers of each still remain intact on the support. However, as the web-speed increases up to about 200 ft./minute and more, the prior art coating like Example 1 is blown off its support under the same degree of force of hot air suitable at slower web speeds. In contrast thereto, all layers of the coated element hardened by the process of the present invention remained intact at 200 ft./ minute showing that all such layers were unexpectedly sufiiciently hardened by selective layer hardening addition, that they exhibited uniform and vastly superior hardening.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

I claim:

1. In a method of coating onto a support at least four superimposed distinct layers comprising hardenable organic hydrophilic colloid and a vinyl sulfonyl alkyl hardener which has the structural formula:

(I) (CH =CHSO CH CH A),,Z

in which A is R y R:N+/- X- or 0-, R being an alkyl of 1 to 4 carbon atoms, X is an acid anion, Z is a polyvalent radical of n valences and n is 17 an integer in the range of from 2 to 6, or

1r [CH CHS 02 CH mlrz where m is 1 to 4 and Z is oxygen or an amine nitrogen, R is lower alkyl or hydrogen, and n is at least 2 the improvement comprising adding said vinylsulfonyl alkyl hardener to at least one, but less than all layers of said hydrophilic colloid, whereby said vinylsulfonyl alkyl hardener substantially uniformly hardens all hardenable organic hydrophilic colloid in said layers.

2. The method of claim 1 in which the hardener is differentially combined in said hydrophilic colloid layers during simultaneous coating thereof.

3. The method of claim 1 in which said hardener is present in a concentration of from about 0.50% to about 3% by weight based upon hardenable material present.

4. In a method of simultaneously coating onto a support at least four hardenable hydrophilic colloid superimposed distinct layers comprising at least one photographic silver halide gelatin layer and bis(vinylsulfonyl methylor -ethyl) ether hardener, the improvement comprising adding to at least one but less than all of the layers of said hydrophilic colloid said bis(vinylsulfonylrnethylor -ethyl) ether hardener, whereby said bis (vinylsulfonylmethylor -ethyl) ether hardener substantially uniformly hardens all hardenable organic hydrophilic colloid in said layers.

5. The method of claim 4 in which the bis(vinylsulfonylmethylor -ethyl) ether hardener is differentially present in said layers during simultaneous coating thereof.

6. The method of claim 4 in which said bis(vinylsulfonylmethylor -ethyl) ether is simultaneously combined in said layers just prior to coating.

7. In a method of coating onto a support, in which the support is resin-coated paper,

hardenable hydrophilic colloid layers which comprise distinct superimposed photographic silver halide containing layers sensitive respectively to blue, green and red, and gelatin-containing interlayers between said blue-sensitive and green-sensitive layers and said green-sensitive and red-sensitive layers, respectively, said layers containing color-forming dye couplers capable of forming, respectively, yellow, magenta, and cyan dyes upon color development, the red-sensitive layer, containing cyan-forming color coupler, being the outermost light sensitive layer and a vinyl sulfonyl alkyl hardener which has the structural formula:

(I) (CHFCHSO CH OH A) Z in which A is RN/, 112N411- or -O-, R being an alkyl of 1 to 4 carbon atoms, X is an acid anion, Z is a polyvalent radical of n valences and n is an integer in the range of from 2 to 6, or

8. In a method of coating onto a support hardenable hydrophilic colloid layers which comprise distinct superimposed photographic silver halide containing layers, sensitive respectively to blue, green and red, said layers containing color-forming dye couplers capable of forming, respectively, yellow, magenta and cyan dyes upon color development, the blue sensitive layer, containing yellowforming color coupler, being the outermost light-sensitive layer and a vinylsulfonyl alkyl hardener which has the structural formula:

(I) (CHFCHSO CH OH A) Z in which A is or --O-, R being an alkyl of 1 to 4 carbon atoms, X is an acid anion, Z is a polyvalent radical of n valences and n is an integer in the range of from 2 to 6, or

(II) (R:

CH OHSOz 1H 112 where m is 1 to 4 and Z is oxygen or an amine nitrogen, R is lower alkyl or hydrogen, and n is at least 2 the improvement comprising adding said vinylsulfonyl alkyl hardener in a concentration range of about 0.50% to about 3% based on the total weight of the gelatin layer to be at least one, but

less than all said hardenable hydrophilic colloid layers, whereby said vinylsulfonyl alkyl hardener substantially uniformly hardens all hardenable organic hydrophilic colloid in said layers.

9. In a method of coating onto a resin coated paper sup port at least four superimposed distinct layers comprising hardenable organic hydrophilic colloid, at least one of said hydrophilic colloid layers containing gelatin, photographic silver halide grains and a color-forming coupler, and a vinylsulfonyl alkyl hardener which has the structural formula:

in which A is [CHFCHSOz on 1.12

where m is 1 to 4 and Z is oxygen or an amine nitrogen, R is lower alkyl or hydrogen, and n is at least 2 the improvement comprising adding said vinylsulfonyl alkyl hardener to at least one, but less than all layers of said hydrophilic colloid, whereby said vinylsulfonyl alkyl hardener substantially uniformly hardens all hardenable organic hydrophilic colloid in said layers. 10. In a method of coating onto a polyethylene coated support hardenable hydrophilic colloid layers which comprise distinct superimposed surface-sensitized convertedhalide photographic silver halide grain containing layers sensitive resepectively to blue, green and red, and gelatin-containing interlayers between said blue-sensitive layers and said green-sensitive and red-sensitive layers respectively, said layers containing color-forming dye couplers capable of forming, respectively, yellow, magenta and cyan dyes upon color development, the red-sensitive layer, containing cyan-forming color coupler, being the outermost light sensitive layer and a vinylsulfonyl alkyl hardener which has the structural formula:

(1) (CH CHSO CH OH A),,Z

in which A is or -O-, R being an alkyl of l to 4 carbon atoms, X is an acid anion, Z is a polyvalent radical of n second red-sensitive photographic silver halide and cyan dye coupler containing layer located on said first red-sensitive layer,

a second gelatin interlayer located on said second reda second green-sensitive photographic silver halide and 1 d t h f fr 2 magenta dye coupler containing layer located on said 2 Zngis an n is an m eger in t e range 0 om i i l t i layer t I i c L .1

a ir gear in in er ayer con aimng areyea 51 ver a located on said second green-sensitive layer and {CHFCHsOlH mhz a first blue-sensitive photographic silver halide and where m is 1 to 4 and Z is oxygen or an amine nitro- 15 zg gz i gg gfigfi zi ggg layer located on Sald R3 is lower alkyl or hydrogen and n is at least a second blue-sensitive photographic silver halide and the improvement in which said vinylsulfonyl alkyl g g g gi gggg i igi layer located on sald 5:35:: i giig gfiggg fgg ggg?figg g bis(vinylsulfonyl methyl-or-ethyl) ether hardener, to ab 3; t 313% based on the total weight of the improvement comprising adding said bis(vmylhardenable hydrophilic colloid, whereby said ig gg g gfgggffiij gg2 53 ig g g g vinylsulfonyl alkyl hardener Substantially unieacii of said red and blue-se iisitive layers in a {$5521 s g gi g zggjg Organic hydroconcentration range of about 0.50% to about 11. In a method of coating onto a polyethylene coated 3% based on i tqtal .welght of the gelatin Support layer, whereby said b1s(v1nylsulfonyl methyl-orhardenable hydrophilic colloid layers which comprise ethyl). 2 5 2? ggi gg ljg i g gg distinct superimposed photographic silver halide con- Organic y r p w y taining layers sensitive respectively to blue, green and References Cited red, and gelatin-containing interlayers between said blue-sensitive and green-sensitive layers and said UNITED STATES PATENTS green-sensitive and red-sensitive layers, respectively, 3,060,052 10/ 1962 Martin 117-83 said layers containing color-forming dye Couplers 2,941,898 6/1960 Wynn ll783 capable of forming, respectively, yellow, magenta 3,508,947 4/1970 Hughes 117-83 and cyan dyes upon color development, the red-sensi- 3,490,911 1/ 1970 Burness et a1. 96-111 tive layer, containing cyan-forming color coupler, 3,369,901 2/ 1968 Fogg et a1 96-111 being the outermost light sensitive layer and 2,652,345 9/ 1953 Jones 915-111 a bis(vinylsulfonylmethyl or ethyl) other harde er, 40 2,761,791 9/1956 Russell 117-34 the improvement in which said vinylsulfonyl ether 2,912,343 11/1959 Collins 96-111 hardener is added to only at least one of said 3 361,436 10/1962 Hi h 96 94 gelatin-containing interlayers in a concentration 3,129,097 4/ 1964 van Hoof 96-111 from about 0.50% to about 3.0% based on the 3,013,173 1 1962 Harriman 117-34 total weight of hardenable hydrophilic colloid, 3,155,509 11/1964 Roscow 117-34 whereby said vinylsulfonyl alkyl hardener sub- 3 5 2 339 5/1971 Martens t a1 96-87 stantially uniformly hardens all hardenable organic hydrophilic colloidin said layers. 12. In a method of coating onto a support having an antihalation under-coat hardenable hydrophilic colloid layers which comprise a first gelatin interlayer located on said support, a first red-sensitive photographic silver halide and cyan dye coupler containing layer located on said first gelatin interlayer,

WILLIAM D. MARTIN, Primary Examiner M. SOFOCLEOUS, Assistant Examiner US. Cl. X.R.

PO-1O5O UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 7 Davted August 29, 1972 Inventor) James L. Graham It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 14, Table I, under the heading'Check A incubatiom H00 07 41 10 07" should read O4--;

Column 18, lines 22-24, "CH =CHSO CH n 2" 3 I should read [CH =CHSO (CH Z.

Signed and sealed this 6th day of February 1973..

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

